This review features state-of-the-artandelectron microscopy (EM) studies of heterogeneous catalysts in gas and liquid environments during reaction. Heterogeneous catalysts are important materials for the efficient production of chemicals/fuels on an industrial scale and for energy conversion applications. They also play a central role in various emerging technologies that are needed to ensure a sustainable future for our society. Currently, the rational design of catalysts has largely been hampered by our lack of insight into the working structures that exist during reaction and their associated properties. However, elucidating the working state of catalysts is not trivial, because catalysts are metastable functional materials that adapt dynamically to a specific reaction condition. The structural or morphological alterations induced by chemical reactions can also vary locally. A complete description of their morphologies requires that the microscopic studies undertaken span several length scales. EMs, especially transmission electron microscopes, are powerful tools for studying the structure of catalysts at the nanoscale because of their high spatial resolution, relatively high temporal resolution, and complementary capabilities for chemical analysis. Furthermore, recent advances have enabled the direct observation of catalysts under realistic environmental conditions using specialized reaction cells. Here, we will critically discuss the importance of spatially-resolvedmeasurements and the available experimental setups that enable (1) correlated studies where EM observations are complemented by separate measurements of reaction kinetics or spectroscopic analysis of chemical species during reaction or (2) real-time studies where the dynamics of catalysts are followed with EM and the catalytic performance is extracted directly from the reaction cell that is within the EM column or chamber. Examples of current research in this field will be presented. Challenges in the experimental application of these techniques and our perspectives on the field's future directions will also be discussed.
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http://dx.doi.org/10.1088/1361-648X/abddfd | DOI Listing |
J Am Chem Soc
January 2025
The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
Ni-catalyzed asymmetric reductive cross-coupling reactions provide rapid and modular access to enantioenriched building blocks from simple electrophile precursors. Reductive coupling reactions that can diverge through a common organometallic intermediate to two distinct families of enantioenriched products are particularly versatile but underdeveloped. Here, we describe the development of a bis(oxazoline) ligand that enables the desymmetrization of -anhydrides.
View Article and Find Full Text PDFInorg Chem
January 2025
State Key Laboratory of Molecular & Process Engineering, SINOPEC Research Institute of Petroleum Processing, Beijing 100083, China.
The ZSM-5 zeolite is the key active component in high-severity fluid catalytic cracking (FCC) catalysts and is routinely activated by phosphorus compounds in industrial production. To date, however, the detailed structure and function of the introduced phosphorus still remain ambiguous, which hampers the rational design of highly efficient catalysts. In this work, using advanced solid-state NMR techniques, we have quantitatively identified a total of seven types of P-containing complexes in P-modified ZSM-5 zeolite and clearly revealed their structure, location, and catalytic role.
View Article and Find Full Text PDFDalton Trans
January 2025
Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming, China.
During the oxygen evolution reaction (OER), metal-organic framework (MOF) catalysts undergo structural reorganization, a phenomenon that is still not fully comprehended. Additionally, designing MOFs that undergo structural reconstruction to produce highly active OER catalysts continues to pose significant challenges. Herein, a bimetallic MOF (CoNi-MOF) with carboxylate oxygen and pyridine nitrogen coordination has been synthesized and its reconstruction behavior has been analyzed.
View Article and Find Full Text PDFRSC Adv
January 2025
Department of Chemistry, Faculty of Science, University of Maragheh P.O Box 55181-83111 Maragheh Iran.
In this study, we present the design, synthesis, and utilization of a covalent triazine framework (CTF) formed by the condensation of , , -tris(4-(aminomethyl)benzyl)-1,3,5-triazine-2,4,6-triamine and 2,4,6-tris(4-formylphenoxy)-1,3,5-triazine on which silica is immobilized (TPT-TAT/silica) as an innovative catalyst for porphyrins synthesis. Under solvothermal conditions, the condensation of triamine and trialdehyde precursors led to the formation of a covalent triazine framework (CTF) with a high nitrogen content. The resulting CTF is characterized by its extensive porosity and elevated nitrogen levels, which are critical for the creation of catalytic active sites.
View Article and Find Full Text PDFChemSusChem
January 2025
TU Dortmund University: Technische Universitat Dortmund, Biochemical and Chemical Engineering, Emil-Figge-Straße 66, 44227, Dortmund, GERMANY.
Platform chemicals from renewable resources with broad applications are highly desirable, particularly for replacing fossil-based monomers. Bifunctional aliphatic ester-aldehydes, accessible via regioselective hydroformylation of unsaturated oleochemicals, can be converted into linear ω-amino/ω-hydroxy esters and dicarboxylic acids-key building blocks for biobased aliphatic polycondensates. However, their success hinges on efficient, economically viable production, with catalyst recycling being critical.
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